Azo dyestuffs



Patented Jan. 14, 1941 UNITED STARS PATENT OFFICE 2,228,374 AZO DYESTUFFS Richard Stiisser, Cologne, and Erich Fischer and Walter Gmelin, Bad

Soden in Taunus, Germany, assignors to General Aniline & Film Corporatlon, a corporation of Delaware No Drawing. Application July 29, 1939, Serial 12 Claims.

The present invention relates to new azo dyestuffs which are capable of forming metal complex compounds; more particularly it relates to azo dyestuffs of the following formula:

radical C1-I=CH, Y stands for alkyl, aryl, COOH and COO.alkyl, Z stands for hydrogen alkyl, halogen, alkoxy, COOH or 8031-1, and 11. means 1 or 0.

Our new dyestuffs are obtainable by combining one or two molecular proportions of the same or different diazo compounds of aromatic amines at least one bearing a metal complex forming group in ortho-position to the amino group with pyrazolones of the following formula:

55 O.GHz.COOH

In Germany August 9, 1938 agents yielding metal in substance or on the fiber the dyestuffs can be converted into the metal complex compounds, whereby the fastness properties, especially the fastness to light, become improved. The dyestuffs yield in general yellow, orange, red and violet shades.

Example 1 2 molecular proportions of 2-diazo-phenoxyacetic acid are coupled in alkaline solution with 1 molecular proportion of 1 .1- [diphenylene- (4.4) bis-[3-methyl-5-pyrazolone] obtained from 4.4- dihydrazino-diphenyl and acetic acid ester. When the coupling is finished the dyestuff is salted out completely by adding some sodium chloride. A brown powder is obtained which corresponds in its free state to the following formula:

OH OH ppm-000E and dyes cotton, viscose and natural silk yellow shades. By aftertreatment of the dyeings with metal salts especially copper salts the dyeings become faster to light and washing. If the dicarboxylic acid of the pyrazolone (obtained by using oxalylacetic ester instead of acetoacetic ester) is used as coupling component a dyestuff is obtained which shows a somewhat greater solubility.

Example 2 1 molecular proportion of 2-diazo-phenoxyacetic acid is coupled in aqueous suspension in the presence of sodium acetate with 1 molecular proportion of 1.1'- [diphenylene- (4.4) l-bis- [3-methyl-5-pyrazolone]. When the dia zo compound has disappeared the mixture is rendered alkaline with sodium carbonate, some pyridine and 1 molecular proportion of 1-diazo-2-hydroxynaphthalene-4- sulfonic acid are added. Thereupon the solution is rendered alkaline with sodium hydroxide, stirred until the diazo compound has disappeared. The dyestuff formed is salted out, filtered ofi, redissolved and dried. It is a dark powder which corresponds in its free state to the following formula:

V S 03H 55 and dyes cotton redbrown shades.

and dyes cotton yellow brown shades. By an aftertreatment with copper salts the dyeing SOaH changes to red-orange-brown and becomes faster to light.

Example 3 2 molecular proportions of l-diazo-2-hydroxynaphthalene-l-sulfonic acid are coupled in sodium hydroxide alkaline solution with 1 molecular proportion of 1.1-[diphenylene- (4.4) l-bis-[3- methyl-S-pyrazolone]. The isolated and dried which corresponds in its free state to the following formula:

and dyes cotton winered shades which, when aftertreated with copper salts, change to violet.

A dyestuff of very similar properties is obtained when the di-pyrazolone obtained from 4.4-diamino-3.3-clichlorodiphenyl is used. By using the di-pyrazolone obtained from 4.4- diamino-diphenyl3.3-dicarboxylic acid a more soluble dyestuif is obtained. If a dyestuff is formed with the di-pyrazolone obtained from dyestuff is a dark powder which corresponds in 4.4-diamino-3.3'-dimethoxydiphenyl it is also its free state to the following formula:

H30.C=N NC-CH3 I HOaS NN o o -N=N SOaH on on and dyes cotton redbrown shades, which, when aftertreated with copper salts, change to bluishred.

Example 4 2 molecular porportions of 1-diazo-6-nitro-2- hydroxy-naphthalene-4-sulfonic acid are coupled in sodium hydroxyide alkaline solution with 1 molecular proportion of 1.1-[diphenylene- (4.4)l-bis-[3-methyl-5-pyrazolonel. The isolated dyestuff is a dark powder which corresponds in its free state to the following formula:

I H3C.C=N l nis- NN 0 6H 011 When aftertreated with copper salts red shades are obtained.

very similar in its properties to the above dyestuff but yields somewhat more reddish shades.

Example 6 2 molecular proportions of 1-diazobenzene-2- carboxylic acid are coupled in a solution, alkaline with sodium carbonate, with 1 molecular proportion of 4.4-bis-[-oxo-3-methyl-A -pyrazolinyl-(lll-stilbene-22'disulfonic acid, obtained from 4.4'-dihydrazino-stilbene-2.2-disuldyestuif is salted out and dried; it is a brown powder which corresponds in its free state to the following formula:

H3O.O=N\ /N=CCEa I S0311 803K OH OH coon H000 Example 5 dissolves in water with yellow coloration and 2 molecular proportions of l-diazoi-acetaminobenzene are coupled in acetic solution with 2 molecular proportions of 1-amino-6-sulfo-2- naphthoxyacetic acid. The aminoazodyestufi is filtered ofi, diazotized in the usual manner and coupled with 1 molecular proportion of 1.l-[3.3'-dimethyl-diphenylene-(4.4)l -bis- [3- methyl-5-pyrazolone] in alkaline solution in the presence of pyridine. The dyestuff is filtered oif, redissolved and dried. It is a dark powder dyes cotton yellow shades which become faster to washing and light, when aftertreated with copper salts.

Example 7 2 molecular proportions of l-diazo-Z-hydroxy- 3.5-dichlorobenzene are coupled in sodium hydroxide alkaline solution with 1 molecular proportion of 4.4-bis-[5-oX0-3-methyl-A -pyrazolinyl-(l) ]-stilbene-2.2-disulfonic acid. The dyestuff is salted out, filtered oh" and dried. It

is a dark powder which corresponds in itsfree state to the following formula:

H3O. C=N CI (:1 H and dyes cotton yellow-brown shades which change to orange and become faster to washing and light when aftertreated with copper salts.

Example 8 2 molecular proportions of 1-diazo-2-hydroxynaphthalene-*l-sulfonic acid are coupled in alkaline solution with 1 molecular proportion of nickel salts into yellowish-red shades and with chromium chloride into brown-red shades.

Example 10 4.4- bis [5-oxo 3- methyl -A -pyrazolinyl (1) stilbene-2.2'-disulfonic acid. The isolated dyestuff is a dark powder which corresponds in its and dyes cotton red-brown shades, which change into red shades and become faster to washing and light when aftertreated with agents yielding copfree state to the following formula: per.

H3C.C=N N=CCH3 l /N CH=GH N\ Hols N=NC=AC C=CN=N S0311 l S 03H S 03H (H) OH H OH H and dyes cotton brown-red shades which change Example 11 to bluish-red and become faster to washing and light, when aftertreated with copper salts.

Example 9 2* molecular proportions of 1 diazo-6-nitro-2- hydroxy-naphthalene-4-sulfonic -acid are coupled in sodium carbonate alkaline solution with 1 mo- OH OCHa Y lecular proportion of 4.4'-bis-[5-oxo-3-phenyland dyes cotton Bordeaux-red shades. The dyeings, when after-treated with copper salts, change into bluish-red shades, with cobalt salts and (ill (I71 2 molecular proportions of 1 diazo-Z-methoxybenzene are coupled with 1 molecular proportion of 4.4-bis- [5-oxo-3-methyl-A -pyrazoliny1- (1) stilbene-2.2-disulfonic acid. The dyestufi is salted out, filtered off and dried. It is a yellow, water-soluble powder, which corresponds to the following formula:

N=CCH; l

o= N=N S0311 S0311 J) G OCHa and dyes cotton yellow shades,

Example 12 1 molecular proportion of l-diazo-Z-hydroxy- 34.5.6-tetrachlorobenzene are coupled with 1 mo- C: S 0311 I H I SOaH OH and. dyes cotton, when aftertreated on the fiber with agents yielding copper, orange shades.

Example 13 I 80311 SOaH and dyes cotton yellow-brown shades, which change to red-orange shades when aftertreated with copper salts.

Example 14 2 molecular proportions of 1-diazo-3.5.6trichloro-2-hydroxybenzene are coupled in sodium carbonate alkaline solution with 1 molecular proportion of MF-bis-[5-oXo-3-carboxyethyl-A pyrazolinyl-(l)]-stilbene-2.2-disulfonic acid. It is a dark powder, which corresponds to the following formula:

l OH 01 on and dyes cotton, when aftertreated on the fiber with copper salts, yellow-brown shades.

Example 15 2 molecular proportions of l-diazo-3.5.6-trichlcro-2-hydroxybenzene are coupled in alkaline solution with 1 molecular proportion of 4. l-bis'- [5-oXo3-methyl A pyrazolinyl -(1) l-stilbene- 2.2-disulfonic acid. The dyestuff is worked up in the usual way. It is a brown powder, which corresponds to the following formula:

I OH

and dyes wool, cotton, viscose and silk orangebrown shades, which become faster to light and washing when aftertreated with copper salts.

We claim: 1. As new products azodyestuffs of the general formula:

wherein RN=N and R1N=N represent radicals of aromatic diazo compounds selected from the group consisting of the benzene and naphthalene series of which at least one bears in ortho-position to the N=Nbridge a metal complex forming group, X stands for a member selected from the group consisting of a bond directly linking two carbon atoms of the nuclei I and II and the bivalent bridge radical Y stands for one of the group consisting of alkyl, aryl, COOH and COO.alkyl, Z stands for one of the group consisting of hydrogen, alkyl, alkoxy, halogen, COOH and SOaH, and n means one of the numbers 1 and 0.

2. As new products azodyestuifs of the general formula:

wherein R-N=N- and R1N=N- represent radicals of aromatic diazo compounds selected from the group consisting of the benzene and naphthalene series of which at least one bears in ortho-position to the N=N-bridge a metal complex forming group, X stands for a member selected from the group consisting of a bond directly linking two carbon atoms of the nuclei I and II and the bivalent bridge radical Y stands for one of the group consisting of alkyl, aryl, COOH and COO.alky1, and Z stands for one of the group consisting of hydrogen, alkyl, alkoxy, halogen, COOH and 8031-1.

3. As new products azodyestuifs of the general formula:

wherein RN=N and R1N=N represent radicals of aromatic diazo compounds selected from the group consisting of the benzene and naphthalene series bearing in ortho-position to the N=Nbridge a metal complex forming group, X stands for a member selected from the group consisting of a bond directly linking two carbon atoms of the nuclei I and II and. the bivalent bridge radical -CI-I=CH-, Y stands for one of the group consisting of alkyl, aryl, COOH and COO.alkyl, and Z stands for one of the group consisting of hydrogen, alkyl, alkoxy, halogen, COOH and SOsH.

4. As new products azodyestuifs of the general formula:

wherein RN:N and R1N=N- are identical and represent radicals of aromatic diazo compounds selected from the group consisting of the benzene and naphthalene series bearing in ortho-position to the N=Nbridge a metal complex forming group, X stands for a member selected from the group consisting of a bond directly linking two carbon atoms of the nuclei I and II and the bivalent bridge radical Cl l l S0311 OH C1 H of the benzene and naphthalene series bearing in ortho-position to the -N==N-bridge a metal complex forming group, X stands for a member selected from the group consisting of a bond directly linking two carbon atoms of the nuclei I and II and the bivalent bridge radical CI-I=CI-I-, Y stands for alkyl, and Z stands for one of the group consisting of hydrogen, alkyl, alkoxy, halogen, COOH and SOaI-I.

6. As new products azo dyestuffs as claimed in claim 2 wherein X of the general formula stands for the bridge radical CH=CH.

'7. As new products azo dyestufis as claimed in claim 3 wherein X of the general formula stands for the bridge radical CH=CI-I.

8. As new products azo dyestuffs as claimed in claim 4 wherein X of the general formula stands for the bridge radical -CH=CH--.

9. As new products azo dyestufis as claimed in claim 5 wherein X of the general formula stands for the bridge radical CH=CH-.

10. As new product the azo dyestufi which corresponds in its free state to the formula:

HO C1 and dyes wool, cotton, viscose and silk orangebrown shades becoming faster to light and washing when aftertreated with agents yielding copper.

11. As new product the azo dyestuff which corresponds in its free state to the formula:

H COOH Y stands for one of the group consisting of alkyl, aryl, COOH and COO.alkyl, and Z stands for one of the group consisting of hydrogen, alkyl, alkoxy, halogen, COOH and SOaH.

COOH

and dyes cotton yellow shades becoming faster to light and washing when aftertreated with agents yielding copper.

12. As new product the azo dyestufi which corresponds in its free state to the formula:

5. As new products azo dyestuffs of the general formula: I

tical and represent radicals of aromatic diazo compounds selected from the group consisting RICHARD s'riissER. ERICH FISCHER. WALTER ,GMELlN. 

